The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies

[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(†)(2) (1) (Pn(†) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved

Bonding in complexes of bis(pentalene)di-titanium, Ti2(C8H6)2

Bonding in the bis(pentalene)di-titanium ‘double-sandwich’ species Ti2Pn2 (Pn = C8H6) and its interaction with other fragments have been investigated by xdensity functional calculations and fragment analysis. Ti2Pn2 with C2v symmetry has two metal-metal bonds and a low-lying metal based empty orbital, all three frontier orbitals having a1 symmetry. The latter may be regarded as being derived by symmetric combinations of the classic three frontier orbitals of two bent bis(cyclopentadienyl) metal fragments. Electrochemical studies on Ti2Pn†2 (Pn† = C8H4{SiiPr3-1,4}2) reveal a one-electron oxidation, and the formally mixed-valence Ti(II)-Ti(III) cationic complex [Ti2Pn†2][B(C6F5)4] has been structurally characterised. Theory indicates an S = ½ ground state electronic configuration for the latter, confirmed by EPR spectroscopy and SQUID magnetometry. Carbon dioxide binds symmetrically to Ti2Pn2 preserving C2v symmetry, as does carbon disulfide. The dominant interaction in Ti2Pn2CO2 is σ donation into the LUMO of bent CO2 and donation from the O atoms to Ti2Pn2 is minimal, whereas in Ti2Pn2CS2 there is significant interaction with the S atoms. The bridging O atom in the mono(oxo) species Ti2Pn2O, however, employs all three O 2p orbitals in binding and competes strongly with Pn, leading to weaker binding of the carbocyclic ligand, and the sulfur analog Ti2Pn2S behaves similarly. Ti2Pn2 is also capable of binding one, two and three molecules of carbon monoxide. The bonding demands of a single CO molecule are incompatible with symmetric binding and an asymmetric structure is found. The dicarbonyl adduct Ti2Pn2(CO)2 has Cs symmetry with the Ti2Pn2 unit acting as two MCp2 fragments. Synthetic studies show, that in the presence of excess CO a tricarbonyl complex Ti2Pn†2(CO)3 is formed, which optimises to an asymmetric structure with two terminal CO ligands and one semi-bridging. Low temperature 13C NMR spectroscopy reveals a rapid dynamic exchange between the two bound CO sites and free CO

Palladium assisted organic reactions-II1 1 Part 1: S.F. Dyke and M. McCartney. Tetrahedron. Ortho-aminomethylstilbene derivatives

Di-μ-chlorobis(N,N-dimethyl-3,4-dimethoxybenzylamine-6-C,N)dipalladium (1b) reacts readily with a variety of styrenes to give good yields of the corresponding o-aminomethylstilbene derivatives